Phenoxy bis(phenyl mercapto)benzenes



United States Patent 3,452,101 PHENOXY BIS(PHENYL MERCAPTO)BENZENES JohnRobert Campbell, Tarkio, Mo., assignor to Monsanto Company, St. Louis,Mo., a corporation of Delaware No Drawing. Application Apr. 22, 1965,Ser. No. 450,198, which is a continuation-in-part of application Ser.No. 379,708, July 1, 1964. Divided and this application Mar. 20, 1967,Ser. No. 642,265

Int. Cl. C07c 149/08; C10m 3/32; C09k 3/02 US. Cl. 260-609 4 ClaimsABSTRACT OF THE DISCLOSURE Certain tris-substituted mixed polyphenylethers-thioethers, containing one ether linkage and two thioetherlinkages, which are useful as functional fluids.

This application is a division of application Ser. No. 450,198, filedApr. 22, 1965, which in turn is a continuation-in-part of applicationSer. No. 379,708, filed July 1, 1964, now abandoned.

This invention relates to mixed polyphenyl ethersthioethers having four,five or six aromatic groups containing at least two sulfur linkages.These classes of etherthioethers can be represented by the structureswhere R is a phenyl group, R is a phenylene group and Y is selected fromO and S but one of the Ys is S and one of the Ys is O;

where R, R and Y have their aforedescribed significance and one to twoof the Ys are 0;

where R, R and Y have their aforedescribed significance and one to threeof the Ys are 0; and

(D) RS RS where R has the aforedescribed significance.

The compounds of this invention are useful as functional fluids of widetemperature ranges of the order of 0 F. to about 650 F. and in variousapplications, such as for force transmission fluids for the transmissionof pressure, power or torque in fluid pressure or torque actuatedmechanisms. Specific examples of such uses are the hydraulic fluids usedto transmit fluid pressure to the ram cylinder of hydraulic presses,devices for the absorption and dissipation of energy, such as shockabsorbers or recoil mechanisms or the transmission of torque throughtorque converter type fluid couplings. The compounds of this inventioncan also be used as damping fluids which are the liquid compositionsused for damping mechanical vibrations or resisting other rapidmechanical movements. The compounds of this invention are also suitablefor use as lubricants between relatively moving mechanical parts, asbases for synthetic greases, as nuclear reactor coolants, as vacuum pumpfluids, as dielectrics, and as the liquid materials in the filters inair conditioning systems. They are particularly well suited for coolingand lubricating gears and bearings in jet engines.

When used as functional fluids, the compounds of this invention can beused per se or in mixtures with other compounds of this invention or inmixtures with polyphenyl ethers and/or polyphenyl thioethers or esters,especially where the instant compounds have relatively highcrystallizing or melting points, The compounds of this invention canalso be used in combination with various addition agents, particularlywhen used as hydraulic fluids or synthetic lubricants, such as oxidationinhibitors, rust and corrosion inhibitors, antifoaming agents,detergents, viscosity index improvers and the like.

Of the above-represented compounds those of structure (A) are preferredbecause their physical properties, especially low crystallizing points,make them usable in a 'wider number of the aforedescribed uses. Also,those compounds containing 50% or more meta linkages are preferredbecause of their lower crystallizing points.

The new compounds of this invention can be prepared by reacting analkali metal salt of a thiophenol with a suitable halide in a suitablecarboxamide solvent, such as N,N' dimethylacetamide or Nmethyl-2-pyrrolidone at temperatures of the order of C.250 C., butpreferably C.200 C. Some of the instant compounds can also be preparedby the Ullmann synthesis by reacting an alkali metal phenate and asuitable halide in the presence of copper at temperatures of the orderof 180 C.-260 C.

The preparation of typical compounds of this invention is illustrated bythe following non-limiting examples.

Example 1 Into a suitable reaction vessel fitted with agitation means,means for measuring reaction mass temperatures and vapor temperatures,heating means, reactant and product inlets and outlets and also fittedwith a reflux condenser, there was charged a mixture of 44 grams ofthiophenol and 26 grams of 86% potassium hydroxide in ml. ofdimethylacetamide. The mixture was heated to obtain the potassium saltof thiophenol and to drive off water of reaction. The mixture was cooledto about 120 C. and 57.3 grams of bis(p-bromophenyl) ether was chargedand the resulting mixture heated at C.- C. for about 14 hours. Thereaction mass was then allowed to cool to room temperature and thenwashed with 200 ml. of 12.5% sodium hydroxide. The organic layer wasthen separated, diluted with benzene, then washed with water and driedunder vacuum. The residue solidified and was crystallized from anisopropanolbenzene mixture to give 47.3 grams of white crystals whichmelt at approximately 82 C.84 C. The product, 4,4-.bis(phenylmercapto)diphenyl ether, i.e., bis(p-phenylmercaptophenyl)ether, analyzed 16.9% sulfur (theory, 16.59%).

3 Example 2 In the manner of Example 1, 44.0 grams of 85.4% potassiumhydroxide, 74.6 grams of thiophenol and 62.9 grams ofbis(m-chlorophenyl) ether were reacted in 425 ml. of dimethylacetamideat a temperature in the range of 150 C.155 C. to provide3,3'-bis(phenylmercapto)- diphenyl ether, i.e.,bis(m-phenylmercaptophenyl) ether, a mobile, colorless liquid which hada boiling range of 237 C.242 C. at 0.4 mm. of mercury.

Example 3 Into a suitable reaction vessel as previously described therewas charged 132 grams of 85% potassium hydroxide and 1000 ml. ofdimethylacetamide. After heating the resulting mixture to about 90 0.,there was added over a period of about 30 minutes 222 grams ofthiophenol and the resulting mixture was then heated to 170 C. to removelow boiling material and then cooled to 160 C. Then, over a period ofabout 30 minutes, there was charged 255 grams of 3,4'4iichlorodiphenylether. The reaction mass was then heated at reflux for about hours,after which dimethylacetamide was stripped and the residue washed twicewith water and the water washes extracted with toluene. Thereafter, thetoluene was stripped and the remaining product fractionated to give3,4'-bis(phenylmercapto)diphenyl ether, i.e., m-phenylmercaptophenylp-phenylmercaptophenyl ether which had a boiling range of 250 C.-254 C.at 0.3 mm. of mercury. Analysis of the product showed that it contained16.5% sulfur (theory, 16.58%). The thus prepared polyphenylether-thioether had a melting point of 732 C.- 73.6 C.

Example 4 Into a suitable reaction vessel there was charged 14 ml. ofwater and 70 grams of 85 potassium hydroxide and the resulting mixturewas heated to 110 C., after which there was added 125 grams of phenol.Then, ml. of toluene was added and the water removed by azeotropicdistillation until a pot temperature of 265 C. was reached. The reactionmass was then cooled to 240 C. and 2 grams of cupric chloride was added.The reaction mass Was then heated slightly at 329 grams of m-(m-phenylmercaptophenylmercapto)phenyl chloride was slowly added. Thereaction mass was then heated at 255 C.260 C. for about 6 hours andquenched. An aqueous layer was then separated, extracted with tolueneand the extract combined with the organic layer. The organic materialwas extracted with water, filtered, and the toluene stripped to give 233grams of 3-phenylmercapt-o-3'-phenoxydiphenyl sulfide, i.e.,m-phenylmercaptophenyl mphenoxyphenyl sulfide, which had a boiling rangeof 236 C.240 C. at 0.1 mm. of mercury.

Example 5 Into a suitable reaction vessel there was charged a mixture of55.1 grams of thiophenol, 32.9 grams of 85.2%

potassium hydroxide and 200 ml. of N-methylpyrrolidone. The air in thevessel was then replaced with nitrogen (which was maintained until thepreparation was completed) and the reaction mass heated to 214 C. toform the potassium thiophenate and remove water. Then, 66.2 grams ofm-bis(m-chlorophenoxy)benzene was charged and the resulting mixture washeated at reflux for about 24 hours. The solvent was then stripped to apot temperature of 240 C. and the residue quenched with 150 grams of 2%sodium hydroxide. After cooling the quenched residue to about 70 C. andallowing an aqueous and an organic layer to separate, the upper aqueouslayer was separated, extracted with benzene and the benzene solutionscombined with the organic layer. The organic material was then extractedwith Water, filtered, stripped of benzene and distilled under vacuum togive 34.7 grams of m-bis(m-phenylmercaptophenoxy) benzene which had aboiling range of 287 C.297 C. at 0.5 mm. of mercury, an index ofrefraction, n of 1.6729 and viscosities, cs., of 284.4 at F. and 12.68at 210 F.

Example 6 Into a suitable reaction vessel fitted with a Dean-Stark trapthere was charged 67.0 grams of m-phenoxyphenol and 22.1 grams of 85 .2%potassium hydroxide. The mixture was heated to C. to dissolve thecaustic, after which 15 ml. of toluene was charged. Heating wascontinued to 245 C. to remove water with distilling toluene and thelatter in turn was separated in the trap and returned to the reactionvessel. After removing about 7 ml. of water the toluene was stripped 01?and 0.5 gram of cupric chloride and 82.2 grams ofm-(m-phenylmercaptophenylmercapto)phenyl chloride were added. Thereaction mass was then heated at about 200 C. for about 16 hours, cooledand then quenched with grams of 4% sodium hydroxide. An aqueous layerand an organic layer were separated and worked up as in Example 5. Thewashed crude product was then fractionated to give the desired product,3-(m-phenylmercaptophenylmercapto)-3-phen0xydiphenyl ether which had aboiling range of 279 C.288 C. at 0.6 mm. of mercury, an index ofrefraction, n of 1.6751 and viscosities, cs., of 275.3 at 100 F. and11.95 at 210 F.

Example 7 In the manner of Example 6, 47 grams of phenol, 28.6 grams of87% potassium hydroxide, 0.7 gram of cupric chloride and 72.7 grams ofm-bis(m-chlorophenylmercapto)benzene were utilized to provide 60.3 gramsof mbis(m-phenoxyphenylmercapto)benzene which had a boiling range of 280C.283 C. at 0.5 mm. of mercury, an index of refraction, 21 of 1.6748 andviscosities, cs., of 357.2 at 100 F. and 12.53 at 210 F.

Example 8 Into a suitable reaction vessel there was charged 34.5 gramsof 87% potassium hydroxy, 23 grams of water, and 111.3 grams ofm-phenylmercaptophenol. The resulting mixture was heated at reducedpressure to remove the water and complete salt formation. Vacuum in thereaction vessel was then displaced with nitrogen, after which 1.0 gramof cupric chloride was charged. Then,

180.9 grams of m-(m-phenylmercaptophenylmercapto) phenyl chloride wasadded slowly at 170 C.-l85 C., after which the reaction mass was heatedat about 200 C. for about eight hours. The reaction mass was then cooledand the organic products obtained by quenching the reaction mass withwater, followed by separation of the organic layer and the washingthereof. After drying, the organic portion obtained was fractionated andthe desired fraction treated with alumina and filtered. The product,3-phenylmercapto 3' (m-phenylmercaptophenylrnercapto)diphenyl ether, hada boiling range of 268 C.-289 C. at 0.08 mm. of mercury, an index ofrefraction, n of 1.6945 and viscosities, cs., of 266.7 at 100 F. and12.37 at 210 F.

a h m (i Into a suitable reaction vessel there was charged 102.4 gramsof m-phenoxyphenol and 102.4 grams of p-phenoxyphenol followed by asolution of 69.0 grams of 87% potassium hydroxide in 45 grams of water.The mixture was heated to remove water, after which 1.75 grams ofanhydrous cupric chloride and 328.9 grams of 3-phenylmercapto-3-chlorodiphenyl sulfide were charged at 174 C.187 C. Thereaction mass was then heated at temperatures of the order of 200 C. forabout seven hours and cooled. The organic product was separated andWashed as in the previous examples, after which it was fractionated toprovide a mixture of 3-phenylmercapto- 3' (m-phenoxyphenoxy)diphenylsulfide and 3-phenylmercapto 3 (p phenoxyphenoxy)diphenyl sulfide, whichhad a boiling range of 266 C.288 C. at 0.08 mm. of mercury, an index ofrefraction, n of 1.6751, and viscosities, cs., of 324.8 at 100 F. and12.88 at 210 F.

Example 10 Into a suitable reaction vessel containing a nitrogenatmosphere there was charged 81.3 grams of thiophenol, 30 grams ofsodium hydroxide and 325 ml. of N-methylpyrrolidone. The resultingmixture was dehydrated and then 130 grams ofbis[m-(m-chlorophenoxy)phenyl] sulfide was charged. The resultingmixture was heated at reflux for about 12 hours, after which the organicportion was obtained by the previously described procedure of waterquenching, benzene extraction, water washing and distillation ofbenzene. The crude organic product was then fractionated to providebis[m-(m-phenylmercaptophenoxy)phenyl] sulfide which had a boiling rangeof 351 C.355 C. at 0.6 mm. of mercury, an index of refraction, 11 of1.6901 and viscosities, cs., of 1700 at 100 F. and 25.06 at 210 F.

Example 11 (a) Into a suitable reaction vessel there was charged about265 grams of sodium benzenethiolate in about 600 ml. ofN-methylpyrrolidone. To this mixture there was added about 181 grams of1,3,5-trichlorobenzene. The resulting mixture was heated at reflux forabout 8 hours, after which the organic layer was obtained by the usualprocedure of water quenching, benzene extraction, washing anddistillation.

(b) In another flask there was prepared a solution of about 133 grams ofpotassium phenate in phenol.

(c) The products from steps (a) and (b) were then combined, a smallamount of cupric chloride was added and the resulting mixture heated atabout 220 C. for about 8 hours, after which the desired product,l-phenoxy-3,S-bisphenylmercaptobenzene, was obtained in the usualmanner.

In a similar manner other compounds of this invention can be prepared.Examples of such compounds are as follows:

o-Phenylmercapto-p-phenoxydiphenyl sulfideo-Phenylmercapto-rn'-phenoxydiphenyl sulfideo-Phenoxy-m'-phenylmercaptodiphenyl sulfidem-Phenoxy-p'-phenylmercaptodiphenyl sulfideo-Phenoxy-p-phenylmercaptodiphenyl sulfidep-Phenoxy-p-phenylmercaptodiphenyl sulfideo-Phenoxy-o-phenylmercaptodiphenyl sulfide o,o-Bis (phenylmercaptodiphenyl ether o-Phenylmercapto-m-phenylmercaptodiphenyl ethero-Phenylmercapto-p-phenylmercaptodiphenyl ether m-(m-Phenylmercaptophenylmercapto m-phenoxyphenylmercapto)benzene[m-(m-Phenylmercaptophenylmercapto )phenyl][m-(mphenoxyphenylmercapto)phenyl] sulfide 3-(m-phenylmercaptophenylmercapto -3 -m-phenylmercaptophenoxy)diphenylsulfide 3,3-bis(m-phenylmercaptophenylmercapto)diphenyl ether3-(m-phenylmercaptophenylmercapto)-3-(m-phenoxyphenoxy)-diphenyl sulfide4- (rn-phenylmercaptophenylrnercapto -4'-(m-phenylmercaptophenoxy)diphenyl ether3-(m-phenylmercaptophenylmercapto)-3'- (m-phenoxyphenylmercapto diphenylether 4,4-bis(m-phenylmercaptophenoxy)diphenyl sulfide4,4'-bis(m-phenoxyphenylmercapto)diphenyl sulfide3-(m-phenoxyphenylmercapto)-3-(m-phenylmercaptophenoxy)diphenyl sulfide3 ,3'-bis (m-phenylmercaptophenoxy diphenyl ether 4-(m-phenylmercaptophenylmercapto -4'- (m-phenoxyphenoxy)diphenyl ether 3-(p-phenylmercaptophenoxy) -3'- (p-phenoxyphenoxy diphenyl sulfide 3-(m-phenylmercaptophenoxy -3 (m-phenoxyphenylmercapto)diphenyl ether3,3-bis(m-phenoxyphenylmercapto) diphenyl ether and 3-(m-phenoxyphenylmercapto -3 m-phenoxyphenoxy) diphenyl sulfide.

In addition to the foregoing compounds, the phenyl and phenylene groupsof such compounds can contain substituents, such as alkyl of 1 to 4carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, phenyl andperfiuoroalkyl of 1 to 4 carbon atoms. Examples of such compounds are asfollows:

4,4'-bis (m-tolyrnercapto) diphenyl ether 3 ,3 -bis (m-tolymercapto)diphenyl ether 2,4-bis m-tolylmercapto) diphenyl ether 3,4'-bis(m-tolylmercapto diphenyl ether 3,3-bis(p-tolylmercapto) diphenyl ether3,3-bis(xylylmercapto diphenyl ether 4,4-bis (xylylmercapto diphenylether 3,4'-bis (xylylmercapto diphenyl ether 3,4'-bism-isopropylphenylmercapto diphenyl ether 3,3 -bis(m-isopropylphenylmercapto) diphenyl ether 2,4-bis(m-isopropylphenylmercapto) diphenyl ether 3,4'-bis(p-tert-butylphenylmercapto) diphenyl ether 4,4'-bis(p-tert-butylphenylmercapto diphenyl ether 3,3 '-bis(p-tert-butylphenylmercapto diphenyl ether 3 ,3 '-bis(2,4-di-tert-butylphenylmercapto) diphenyl ether 3,3 -bis3-chlorophenylmercapto) diphenyl ether 4,4-bis 3-chlorophenylmercapto)diphenyl ether 3,3'-bis(m-trifluoromethylphenylmercapto) diphenyl ether4,4-bis(rn-trifiuoromethylphenylmercapto) diphenyl ether3,4-bis(m-trifiuoromethylphenylmercapto) diphenyl ether2,3'-bis(In-trifluorornethylphenylmercapto)diphenyl ether 3,3-bis(p-trifluoromethylphenylmercapto diphenyl ether3,3'-bis(o-trifluorornethylphenylmercapto)diphenyl ether3,3-bis(m-methoxyphenylrnercapto)diphenyl ether 3,4'-bis(rn-isopropoxyphenylmercapto) diphenyl ether 3 ,4'-bis(m-perfiuorobutylphenylmercapto) diphenyl etherZ-(m-tolyloxy)-2'-pheny1rnercaptodiphenyl sulfide2-(p-tolyloxy)-3'-phenylrnercaptodiphenyl sulfide 2- (o-tolyloxy-4-phenylmercaptodiphenyl sulfide3-(m-to1yloxy)-3'-phenylmercaptodiphenyl sulfide 3- (m-tolyloxy4'-phenylmercaptodiphenyl sulfide 4- (m-tolyloxy)-4'-phenylrnercaptodiphenyl sulfide 3-xylyloxy-4-phenylmercaptodiphenylsulfide 3-xylyl0xy-3-phenylrnercaptodiphenyl sulfide3-phenoxy-3-(m-tolylmercapto) diphenyl sulfide3-phenoxy-4'-(m-tolylmercapto)diphenyl sulfide2-phenoxy-3-(p-tolylmercapto)diphenyl sulfide 3-phenoXy-4'-(m-isopropylphenylmercapto) diphenyl sulfide 3-phenoxy-3-(m-isopropylphenylmercapto) diphenyl sulfide 3-m-toloxy-3(m-isopropylphenylrnercapto) diphenyl sulfide 4-m-trifluoromethylphenoxy) -4'-pheny1rnercaptodiphenyl sulfide 3(m-trifiuoromethylphenoxy) -4'-phenylmercapto diphenyl sulfide2-(m-trifluoromethylphenoxy)-3-phenylmercaptodiphenyl sulfide 3-m-trifluorornethylphenoxy -3'-phenylrnercaptodiphenyl sulfide3-(p-chlorophenoxy)-3'-phenylmercaptodiphenyl sulfide3-(m-brornophenoxy)-4'-phenylmercaptodiphenyl sulfideBisIm-(m-chlorophenoxy)phenyl] sulfidern-Bis[3-(p-methylphenylmercapto)phenoxy1benzene m-Bis 3-(m-trifluoromethylphenoxy phenylmercapto 1- benzene m-Bis [3 rn-bromophenoxy) phenylme rcapto] benzene 3 ,3 -bis [m- (p-methylphenylmercapto phenoxyi] diphenyl sulfide 3 ,4'-bis [mp-methylphenylmercaptophenoxy] diphenyl sulfide 3 p-xenyloxy) -3 '-phenylmercapto diphenylsulfide 3 ,3 '-bis (m-phenylrnercaptophenoxy) biphenyl and 1-(o-xeny1oXy)-3, S-bisphenylrnercaptobenzene While this invention hasbeen described with respect to various specific ex'amples andembodiments, it is understood that the invention is not limited theretoand that it can be variously practiced within the scope of the followingclaims.

The embodiments of the invention in which an exclusive properly orprivilege is claimed are defined as follows:

1. A compound represented by the structure where R is selected from thegroup consisting of phenyl and substituted phenyl in which thesubstituents on said substituted phenyl are selected from the groupconsisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbonatoms, halogen and perfluoroalkyl of 1 to 4 carbon atoms.

2. A compound of claim 1 where R is phenyl.

3. 1-phenoxy-3,5-bisphenylmercaptobenzene.

4. 1-phenoXy-2,4-bisphenylmercaptobenzene.

References Cited UNITED STATES PATENTS 3,102,916 9/ 1-963 Reifschneider260-609 CHARLES B. PARKER, Primaly Examiner.

D. R. PHILLIPS, Assistant Examiner.

US. Cl. X.R. 2S24S, 67, 73

